Lubricating composition



Patented Sept. 23, 1952 ,-sign,or. .to Aluminum Company of America, Pittsburgh," 2a., a corporation of Pennsylvania,

' JNii -Drawing. Application December 111949181:-

' rial'No.'133,685. In Canada-June 10,1947

7 a 1 a iflZhiszinventioncrslates :todmprovedlubricants, SuGhEaSLOflS'figIBaSeS or, semiefluid oils,-contaimng as amajor zlubricating component hydrocarbon oil of naturaltzorysyntheticr origin. in particular, the:invention'relatesgto lubricating compositions of; this? type: ;having:::improved extreme pressure characteristics I p .1Requirements:uponzlubricants,by developments in :mechanical;=;design=are rigid and drastic, In manysinstances pressures atbea-ring surfaces are higher; than those; which petroleumoils Will norma1ly"withs,tand..: Illustrative -;are the conditions encountered .1 (in. 1 :the lubrication of automotiv hypoidzgearstzheavily "loaded mill pinion gears, naval turret gearslandl the like. Inma ny .machines operation is; at. least in1part,*underconditions of thin film lubricationror llnder similar conditions Where film strength oi-linessand antiwear.- characteristics :of high order are required of the lubricating medium.

-'Ihe-principalaob-jectof: this; invention is; the provision; of a; new compositionof matter consisting: of a .eom-pounded lubricating .product possessing extreme pressure characteristics of a high order. Further'objects include theprovision of .a .;compounded lubricantcontaining as a major hydrocarbon1lubnicatingcomponent which maywbe! oil: "or. grease iofl natural or synthetic originathe :lubricanthaving a superior combination: of high: film. strength; oiliness 1 and anti-wear characteristics.

;:In. accordance with this. invention these objects 1 3 Claims. (01. 25249.6)

are achieved in substantial part by providing a lubricant; the: essential lubricating components ofwhich; are a. major. amount; oi a hydrocarbon lubricating COHIPQIIGD-tzWhiCh may be oil or grease and aminorlamountnof a body of'boronfluoride and a substance; selected from. .the class cconsisting of aliphatic, aromatic and heterocyclic monoand.-polyamines;emino alcohols and amides more specificallycdescribed below. The proportion of this body. tot .-the hydrocarbon" component i should bet-such, -.however,. that the. mixture contains at least Q;001%:by :Weight-of :boron fluoride (-31%) while; on; the other hand, more; than 3% does. notnimprove 'theylubricant. Within this range it-.has :been" found that the best resultstare: ob-. tained ,byxproviding from. 0.1 to 1.0. :percent of boron :fluoridezin l the final lubricant mixture. The choice. of the particular body to be employed andtitssboron fiuoride content will of course depend on such matters as cost, ease'of mixing and themature ofothelubrication,problem; 1 v

--'iThe principal advantages andeiiec'tivene'ss of this :new 7 compounded lubricant are I maintained when, inaddition .to the abovementionedessem tial components there-are likewise. present in the lubricating composition other components added to improvasomexspeoific characteristic or property thereof; suchas'viscosity, pour. point,..oili-.

ness, flow, anti-wearcharacteristics,tfilmstrength or the like, the effect of the defined. boron .fiuoride-containing body' -when similar, beinglargely additive. Such diluents oriadditions may therefore, forthe purposes. of this inventiombe-regarded as a: non-essential; portioni-of the composition, regardless p of their. specific beneficial o'r functional effect .The same may be=said of substances known as extreme. pressure-additives, such as substances composed ofchlorine, sul-' phur or lead containing compounds -or;ma'teria'ls, it being observable .that the presence of the defined boron' fluoride-containing. -bodiesis *effective to increase .theeXtreme-pressure characteristics :of' the compositions even when other extreme pressureadditives are present.

*The organic BFsbodygwhich in accordance with: this invention is blended with the hydrocarbon. component, may be prepared in various Waysbut is, for the most part, convenientlyprepared by exposing the amino, 4 amino alcohol or amide to-direct contact with-gaseous BFa. This can be easily accomplishedunder--ordinary atmospheric pressure by bubbling-thegaseous BFs through the amine, amino alcoholor amidein a. liquid state.- If the organic material is not; liquid at room temperature it should-b heated to and maintained at a -temperature slightly above itsmelting' point, say 5 or 10 'C."*'A1thOl1'gh the rate of flow of the gas is not --critical' with respect to-for-mation ofthe -BF3 additive yet-the fiovv. should he -controlled to avoid --undue---lo'ss; The ra'tefof acceptance'of the BF's'by the-amine, amino alcohol oramide is improved ifthe man is stirred as the gas is introduced. Theamount ot'BFs -accepted by the amine;- amino alcohol or amide is indicated by: the increase in weight ofth'e treated mass. I The introduction'ofthegas may therefore be continued until a predetermined-increase =in-=weight, short ;of saturation, has been obtained or the flovvyoi? gas-may beprolonged until no further increase in weight is observedat which-poin-t the-amine, amino alcohol oramide is considered to=besaturated-with 315's. Generally, it is -most convenient tofollow the latter procedure. In --both cases, however, the length of time required to reach theend point can be easily determined for the materiabbeing treated and thus-make it po'ssible to introduce the desired amount of BF3 Withouthaving to test a charge at intervals during the period of treatment. Although each amine, amino alcohol or amide may have a different saturation point or the desired BFs content may differ for various materials, this does not detract from the value of the BFs-containing body in improving the load bearing quality of a hydrocarbon lubricant.

Other methods of introducing BFs can be employed, of course. For example, the amine, amino alcohol or amide may be exposed to the gas at higher temperatures and pressures and thus shorten the time required to introduce the desired amount of BFS. Naturally, the temperature and pressure should be such that the amine, amino alcohol or amide is not decomposed to any substantial degree. Another method of contacting the organic material with BFs is to add compounds to it which can be decomposed with the release of BFs. Such compounds as NH4BF4, BF3-NH3, the heavy metal fiuoborates or even otherorganic materials previously treated with BFa may be employed. To efiect decomposition it is usually necessary to heat the mixture of amine, amino alcohol oramide and the BF3- containing substance. Further, it may be desirable to remove any residues resulting from the decomposition.

The amount of BFs that can be introduced into difierent amines, amino alcohols or amides will vary, as-mentioned above, however, from to percent by weight is preferred where the saturation point permits it. In any case, the amines, amino alcohols or amides should be treated with sufiicient fluoride to provide the desired BFa content in the lubricating composition as only a minorproportion of the additive is employed.

The resultant product may, in some instances, be an actual compound, there being some evidence to indicate that such is its nature, or it may be an additive or coordinate compound or even a solution or dispersion. I prefer, however, to term the product a body'or composition consisting essentially of a substance selected from the class consisting of aliphatic, aromatic and heterocyclic monoand polyamines, amino alcohols and amides and BFs and, therefore, not to characterize the state of association of the fluoride and the organic substance. In any event, the aliphatic, aromatic and heterocyclic monoand polyamines, amino' alcohols and amides act as acceptors of BFa to produce abody or substance having positive advantages as an additive in lubricating compositions.

The following list of amines, amino alcohols and amides is illustrative of the class which when treated with BFa produce the bodies just described: monoamines such as those of propyl through octadecyl and diethylhexylamine; symmetrical and unsymmetrical (mixed) alkyl polyamines such as propyl through octadecyl diand triamines, 1,4 diaminobutane, 1,12 diaminododecane, ethylene diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and propylenediamine; V aminoethanols such as monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, aminoethylethanolamine, methyldiethanolamine, phenylethanolamine, phenyldiethanolamine and ethylphenylethanolamine, also triisopropanolamine, ethyl phenyl diisopropanolamine, condensation products of high molecular weight amines with polyglycol derivatives of ethylene oxide and its homologues; amides and imides such as acetamide through octadecylamide, amides of the dicarboxcyclic acids, ox-

amide, succinamide, octadecylacetamide, n-propyloleamide, methylolstearamide, methylenedistearamide, benzylacetamide, methyl x naphthylamide, adipamide, succinimide, stearanilide, benzamidine, acetamidine, phenetidide, tolinidide, hydroxyacetanilide, acetocetanilide, chloracetocetanilide, dichloracetoacetanilide and ac etoacet-o-toluidide; aromatic amines such as phenyltridecylamine, benzymethylamine, aminodiphenylamine, phenylheptadecylamine, and acetyl p-phenylenidiamine; heterocyclic amines such as pyridine and oxazoles, the derivatives and substituted derivatives of the oxazoles such as dihydrooxazole and its alkyl substituted derivatives, for example 2 tridecyl 4 (hydroxymethyl) -4-ethyl. oxazoline and 2 hendecyl oxazoline; as well' as other amines such as 2-hydroxyethylamine,heptadecamethylenimine,hexamethylenimine, lfi-hydroxyhexadecylamine, octadecadienylamine, phenyl biguanide, pyrinidine, 2-sub'stituted-4-amino-6-N 'phenyl-amino-1,3,5- triazine, 12 (dibutylamino) dodecananidine, lauranidoxine, hydroxamic acids of propionic, lauric and stearic acids, phenylhydrazides of lauric and stearic acids, piperidides of acids, aminonaphthol, aminophenylglycine, aminoquinoline, aniline, anisidine, arabinose phenylhydrazone, benzoylhydrazine, benzoylthiourea, benzylhydroxylamine, 'carbohydrazide, acetaldazine, aoetaldoxime; acetaldehyde phenylhydrazone, acetanilide, acetophenone phenylhydrazone, acetyl phenylhydrazine, aminopropionic acid, aminoacetophenon'e, aminoanthraquinone, aminoazobenzene, aminodibutylaniline, aminoethylacetamilide, urea, quinoline, morpholine,

tetraethanolammonium hydroxide and phenyl methylpyrazolone.

The introduction ofthe BFa into the amine, amino alcohol or amide may change the color thereof, often making it darker. Also, the liquid amine, amino alcohol or amide may become thicker as the introduction of BF: proceeds and the melting point of the end product may be higher than that of the original amine, amino alcohol or amide. Such changes do not affect the advantages gained from the presence of the BFa-containing bodies in a hydrocarbon lubricant, certainly the results of the invention do not depend'upon or are responsive to any peculiar chemical or physical qualities of the BFa-containing additive, rather they depend upon the admixture of the additive with the hydrocarbon lubricant. V i

The action of these organic BFs bodies in a hydrocarbon lubricant is positive and specific to increase the load bearing capacity of the lubricant and, in many instances, to definitely improve its anti-wear characteristics. The amount of these organic BB5 bodies necessarily present to produce these specific effects is very small. The amounts used, should in any case, as mentioned above, provide at least 0.001% by weight of BF3 in the final mixture.- The amount of any given BF3- containing body desirably present to produce optimum effects in any particular hydrocarbon lubricant can be readily determined by simple trial, the optimum usually being found within the range of (Lite 5 percent by weight of the amine, amino alcohol or amide BFa body. Amounts below about 0.01 percent by weight often do not produce sufficient efiect to be usually characterized as commercial, but the effect produced is such as to be useful under'exceptional conditions. One may use a relatively small amount of an additive containing a substantial quantity of BFs or a larger amount 0f:the: same" or-ranother additive which contains .a smaller proportion of BFs to introduce a given .quantity of BF3 into the hydrocarboncomponentf. In any event', the organic BFafaddiinvention. general, "torque and. temperature valuespbtained during :thesatests. indicated: that the organic lBEaabody improved friction qualities and {observationssimultaneously made. indicated The machine on which the tests were run had a capacity of 4500 pounds. Where this capacity was approximated or exceeded the failure load is the improvement obtained by the practice of this 75 tive forms .a'. minor amount orproportiomofthe o increasesLinanti-wearcharacteristics. I lubricating composition. "i LIIIGQIBDOHDd-iIIgllIbIiQaHt.OOmpOSitiOIls of the The load bearing qualities of a lubricant may typeherein described .andlclaimed the organic BF: be relatively determinedby various methods. The additive may merelybe mixed withthe hydrocarmethod used to obtain the comparative dataherehon-lubricants, .the properties ofrwhich areto be inafter set forth is practiced on a Falex machine 10 improved. Wheretheadditive is insoluble in the andlconsists in submittin small quantities of the lubricantpr-v it is desired" to incorporate therein lubricant to the action of arotatingsteel journal amounts in excess of solubility, emulsions or disrotated in contact-with two V-shaped bearing persions mayzbezprepaited.;accor,ding to known blocks- During-testing measurablefpressurewas principles. applied to.the=rotatingjournal-.byuse of'tan auto- This application is a continuation-.in-part-of matic loading device. The two bearing blocks my prior application Serial No. 714,911 filed De and the journal were submerged in the lubricant cember 7, 1946, and entitled Lubrication Composisample throughout the tests. In each test load tion, now abandoned. was applied and allowed to reach 500 pounds; at Having thus described my invention and the this load the journal was then run for 5 minutes; known advantages thereof, I claim: thereafter the load was gradually increased until 1. A lubricating composition comprising a lubrication failure occurred. The load at the major proportion of ahydrocarbon lubricating time of failure is designated as the failure load. oil blended with a minor proportion of a body In general, the failure loads are reproducible consisting essentially of asubstance selected from within 150 pounds at lower pressure and 300 the class consisting of aliphatic, aromatic and pounds at higher pressure; the results are not abheterocychc menoand polyammes, ammo alcosolute but are comparative with a standard run hols argd amides anddBFaio said body being preunder the same conditions. In the tests by which pared y exp ng sai su stances to direct conthe results set forth in the following table were tact with a substance selected from the class 0 secured, the hydrocarbon oil was in all cases the B0 slstmg of ,igdaseous BB5 anti? decomp ble comsame, being a straight mineral oil. In all cases P0011 S yie 111g gaseous B -3 and being present 1 percent by weight of additive was present in the in tl q o 'g i g lubricatilggbcomposition oil. The additive had been prepared by passing C011 @1115 from 0 0 3 Der Gen y weight of BFc through the amine, amino alcohol or amide 3, aid lubricating co po iti n D0SeSSing BX- until the weight of the body became substantially g e pressure eharacterlstlcs superior to those constant, that is, the organic material became exhlblted by a s r l pos t p m wh ch th saturated with the BFs, as has been described 11111101 proportlon aforesald COIISISBS 0f f hereinabove. Each comparative test was run on stallces selficted from the c1 a$$ Conslstlng of two samples, one sample being the oil containing ammes, m alcohols and a n 1 percent by Weight f an amine, ammo alcohol. 40 2, A lubricating composition comprising a or amide. the other sample being the 011 containmi ls; g g rtig of a v b o l ag ge ing the same weight of aBFa-c0ntaining body. In 01 en 8 W1 a m nor propor 10H 0 a O y the first column of the table the nature of the adconsistillg a ly of an oxazole and BFa, said ditive is set forth, in the second column is listed y bemg P p y P g d O OIe t the BF: content of the treated material, in the direct contact with a substance selected from the third column is the BF3 content of the lubricant, class conslsfiilg gaseous BFH and decomposable in the fourth column the failure load in pounds compounds yleld g ous BFsand being p is given and in the fifth column is shown the perent in such amount that the lubricating composicentage increase in failure load caused by the tion contains from 0.001 to 3 per cent by weight presence of the BFa-containing body. of BFa, said lubricating composition possessing Percent Percent Failure Percent- Add1tlve BF: in BF! in Load in age Additive Lubricant Pounds Increase 344 0 269 Tetraethylene pentam ne 13 Tetraethylene pentamlne BF3 1, 190 Monoisopropanolamlne 850 35 Monoisopropanolamine BF3. 1, 150 2 Amino, 2 methyl, 1,3 propanediol 850 29 2 Amino, 2 methyl, 1,3 propanediol BFa. 1, 100 Triisopropanolanline -r 850 229 Trlisopropanolemine BF 2, 800 Urea 950 178 Urea BFa.- 2,650 Quinoline 1,050 116 Qumollne BF; 2, 270 Morpholine 650 Morphollne BF: 33. .33 l, 270

Greater than.

extreme pressure characteristics superior to those exhibited by a similar composition, in which the minor proportion aforesaid consists of an oxazole.

3. A lubricating composition comprising a major proportion of a hydrocarbon lubricating oil blended with a minor proportion of a body 7' consisting essentially of an ox azoline and BFa', said body being prepared by exposing said o'xazoline to direct contact with a substance selected from the class consisting of gaseous BFa and decomposable compounds yielding gaseous BF3 and being present in such amount that the lubricating composition possessing extreme pressure characteristics superior to those exhibited by a similar composition in which the minor proportion aforesaid consists of an oxazoline.

EGBERT MASON KIPP.

REFERENCES CITED The following references are of record in the rile of this patent: I

Number Number 10 645,202 645,425

UNITED STATES PATENTS Name Date Graves Sept. 8, 1936 Shoemaker June 6, 1939 Miller ,June 16, 1942 Miller July 28, 1942 FOREIGN PATENTS Country Date Great Britain Jan. 9, 1948 Great Britain Jan. 9, 1948 OTHER REFERENCES Boron Trifiuoride and its Derivatives-Booth 15 et 21., John Wiley and Sons1949, pp. 3-49. 

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTION OF A HYDROCARBON LUBRICATING OIL BLENDED WITH A MINOR PROPORTION OF A BODY CONSISTING ESSENTIALLY OF A SUBSTANCE SELECTED FROM THE CLASS CONSISTING OF ALIPHATIC, AROMATIC AND HETEROCYCLIC MONO- AND POLYAMINES, AMINO ALCOHOLS AND AMIDES AND BF3, SAID BODY BEING PREPARED BY EXPOSING SAID SUBSTANCES TO DIRECT CONTCT WITH A SUBSTANCE SELECTED FROM THE CLASS CONSISTING OF GASEOUS BF3 AND DECOMPOSABLE COMPOUNDS YIELDING GASEOUS BF3 AND BEING PRESENT IN SUCH AMOUNT THAT THE LUBRICATING COMPOSITION CONTAINS FROM 0.001 TO 3 PER CENT BY WEIGHT OF BF3, SAID LUBRICATING COMPOSITION POSSESSING EXTREME PRESSURE CHARACTERISTICS SUPERIOR TO THOSE EXHIBITED BY A SIMILAR COMPOSITION IN WHICH THE MINOR PROPORTION AFORESAID CONSISTS OF SAID SUBSTANCES SELECTED FROM THE CLASS CONSISTING OF AMINES, AMINO ALCOHOLS AND AMIDES. 